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Pyrolysis 72 (2004) 97–102
Pyrolysis of municipal plastic wastes for recovery of gasoline-range hydrocarbons
Department of Chemical Engineering, Selcuk University, Konya, Turkey Accepted 2 March 2004 Available online 18 May 2004
Abstract This paper describes non-catalytic pyrolysis of plastic waste materials. Three types of waste plastics were used in this study: polystyrene (PS), polyethylene (PE) and polypropylene (PP). Under pyrolysis conditions, plastic wastes can be decomposed into three fractions: gas, liquid and solid residue. The liquid products are usually composed of higher boiling point hydrocarbons. In order to obtain useful gasoline-range hydrocarbons from the pyrolytic oil, fractional distillation is preferred for product separation. More valuable chemical raw materials including benzene, toluene and other condensed aromatic hydrocarbons may be obtained by reﬁning the pyrolytic oil. The results showed that waste PS yielded higher liquid, and waste PE and PP yielded higher gaseous products. The dominant pyrolytic liquid product of PS waste was styrene. © 2004 Elsevier B.V. All rights reserved.
Keywords: Plastic waste; Plastic pyrolysis; Gasoline-range hydrocarbons; Re-reﬁning; Municipal
1. Introduction In recent years the consumption of plastics has increased drastically; as a consequence the responsible disposal of plastic wastes has created serious social and environmental arguments . Recycling and re-reﬁning are the applicable processes for upgrading of petroleum based plastic wastes (PBPWs) by converting them into reusable products such as gasoline and heavy oil. PBPW is a source of useful energy (fuels) and/or chemicals and has many advantages from an ecological point of view . Possible acceptable processes are cracking and pyrolysis. The cracking process yields a highly unstable low-grade fuel oil which can be acid-corrosive, tarry, and discolored along with a characteristically foul odor. The pyrolysis process consists of the thermal degradation of the wastes in the absence of oxygen/air. Plastics pyrolysis may provide for disposal of plastic wastes with recovery of valuable gasoline-range hydrocarbons. In pyrolysis, the polymeric materials are heated to high temperatures, so their macromolecular structures are broken down into smaller molecules and a wide range of hydrocarbons are
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formed. These pyrolytic products can be divided into a gas fraction, a liquid fraction consisting of parafﬁns, oleﬁns, naphthenes and aromatics, and solid residues. Pyrolysis appears to be a technique which is able to convert PBPWs into gasoline-range hydrocarbons . All human and industrial processes produce wastes, that is, normally unused and undesirable products of a speciﬁc process. Plastic wastes can be classiﬁed as industrial and municipal plastic wastes (MPWs) according to their origins; these groups have different qualities and properties and are subjected to different management strategies. The municipal solid waste (MSW) products include paper, containers, tin cans, plastics, aluminum cans, and food scraps, as well as sewage. MPWs normally remain a part of MSWs as they are discarded and collected as household wastes. Plastics usually account for about 7% of the total MSW by weight and much more by volume. In order to recycle MPWs, separation of plastics from other household wastes is required. The waste products of industry and commerce include plastic, paper, wood, and metal scraps, as well as agricultural waste products . Table 1 shows the contents of municipal solid waste. There are four major methods for conversion of organic wastes to synthetic fuels: (1) hydrogenation; (2) pyrolysis; (3) thermal and/or catalytic cracking, (4) gasiﬁcation: and (5) bioconversion [5,6].
0165-2370/$ – see front matter © 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.jaap.2004.03.001
A schematic representation of the apparatus used is shown in Fig. and (7) collection vessels for liquid products. The crude synthesis gas is injected into exhausted oil reservoirs.0 mm and o. lowered the condensate. Catalytic decomposition increased the amount of gaseous products. Anal. i. For thermogravimetric analysis.8 2.5 10. Plastics wastes are converted into synthesis gas. Polystyrene (PS). 963 and 1008 K in a technical-scale ﬂuidized bed reactor . The heating was carried out from 298 to 1025 K in nitrogen stream. The inﬂuence of zeolite catalytic upgrading of the pyrolysis gases derived from the pyrolysis of polyethylene has been investigated .98 A. . At the highest pyrolysis temperature of 1008 K.3 8. Plastic sample was weight for run 1. They were shredded into 3 mm × 5 mm size. Traditional recovery methods have generally concentrated on recycling of materials or incineration for energy . The oil reservoir has ﬁltering capacities . Netzch 429/409 thermal analyzer was used. The decomposition of a polymer mixture over HZSM-5 and orthophosphoric acid modiﬁed (PZSM-5) zeolite catalysts has been comparatively studied . 17.d. The most common test method for cracking is described in ASTM D-1693 “Standard Test Method for Environmental Cracking of Ethylene Plastics. 1. Pyrolysis 72 (2004) 97–102 Table 1 Contents of municipal solid waste (wt. oil and a solid residue which all have the potential to be further utilized . (3) thermocouple.2 Upper limit 50.8 0. (1) Digital balance. thermogravimetric analysis (TGA) and pyrolysis runs were carried out. Simpliﬁed experimental device for plastic waste pyrolysis. Appl. 1. toluene and xylene (BTX).% of an oil.9 1. while the liquid products contained mainly aromatic hydrocarbons.7 21. (5) steel reaction vessel. Polyethylene was pyrolysed in a ﬁxed bed reactor and the pyrolysis gases passed to a secondary reactor containing Y-zeolite or zeolite ZSM-5 catalyst.00 g and Fig.2 11.% of the pyrolysis product.8 Literature reports several papers on pyrolysis of plastics [1. The pyrolysis experiments were carried out in a stainless steel tube with height 76. The polyethylene was pyrolysed at 775 K.2 10. Concern over the volumes being created has lead to a number of governments introducing new legislation for its recovery as a resource. In order to assess the thermal behavior of the plastic samples. (2) temperature transmitter.0 mm.4 mm. The gaseous products contained a large C3 fraction. At 911 K over 50 wt.2 18. Demirbas / J. Isothermal conditions and a controlled heating program of 10 K/min were used.” 2. The Y-zeolite produced signiﬁcantly greater concentration of aromatic hydrocarbons in the derived oils compared to when zeolite ZSM-5 catalyst was used.d. In this way atmospheric pollution is avoided.8 7.% of the pyrolysis product was oil with a boiling point less than 538 K. (4) external heater. about the half of which consists of benzene.7–16]. (6) ice baths. The oils consisted of mainly aliphatic compounds represented by alkadiene. polyethylene (PE) and polypropylene (PP) wastes were collected from landﬁll in the form of cattery. and changed their composition with respect to the non-catalytic at the same pyrolysis temperature. the main product was highly aromatized oil.0 1.0 1. Pyrolysis is a tertiary recycling process and has an ability to provide three end products: a gas. 19. alkene and alkane hydrocarbons and their branched chain derivatives. Experimental Three types of waste plastics were used in this study.2 2.6 1. Plastic waste has become an increased problem in many industrialized countries. The numerical simulations of the linear pyrolysis of cellulosic and polyethylene waste were investigated . The polyvinylchloride (PVC) waste was pyrolyzed at 911.6 2.% of total) Component Paper waste Food waste Plastic matter Metal Glass Textile Wood Leather and rubber Miscellaneous Lower limit 33. the BTX-aromatics content is about 20 wt. The experiment at 963 K yielded about 40 wt.3 7.
Table 2 shows the product Fig. as well as the presence of halogen and other hetero-atoms in the polymer chains .0 42. the chain defects of the polymers.18]. and 0.A. The behavior of PE or PP and PS shows one main distinct weight loss step. 55. The differences in TG curves could obviously be attributed to the macromolecular structure and pyrolysis mechanism. PS thermal degradation is a radical chain process including initiation. Conversion of plastic wastes into gasoline-range hydrocarbons via pyrolysis in the absence of a catalyst has been reviewed by Kaminsky [19.6 46.%. The products were analyzed mainly in liquid state using a Fisons Ins. While initial MW increases from 2200 to 50. Random-chain scission. PP and PS wastes.8 1. Results and discussion PE and PP are the main components of MPWs.25 i. Some chromatographic analysis of the gaseous products was also made.6 1. ZB-625 capillary column. .20]. 2. 2. Pyrolysis 72 (2004) 97–102 99 pyrolyzed in the tube. condensables as tarry liquids and wax degradation products and solid residue. For each run. Degradation ﬁnished between 720 and 760 K for the plastic wastes. The pyrolysis products were collected within three different groups as non-condensable gaseous products.d.000 the yield of styrene increases from 67 to 78 wt. Four types of mechanisms of plastics pyrolysis have been Different mechanisms are to some extent related to bond dissociation energies.8 49. The TG behaviors of PE and PP are similar. which show that both of them have a constant degradation behavior at the involved temperature range.4 48. PP and PS wastes are depicted in Fig. Heating rate: 10 K/s.6 1. and the aromaticity degrees. The simple thermocouple (NiCr–Constantan) was placed directly in the pyrolysis medium. The thermogravimetric (TG) curves for PE. The pyrolysis of PS occurs by both end-chain and random chain scission and the monomer recovery is only some 45% . Appl. The pyrolysis of PE and PP occurs through the random-chain scission mechanism and a whole spectrum of hydrocarbon products is obtained . PE thermal degradation consists of free radical formation and hydrogen abstraction steps . Heat to tube was supplied from external heater and the power was adjusted to give an appropriate heat up time. Cross-linking. Pyrolysis of plastics has been studied extensively in the past [17.4 – – 64. . 30 m long. 3. but PS is different. The product distribution from PS pyrolysis depends on initial molecular weight (MW) of the PS sample .% of waste) Waste Pyrolysis temperature (K) 1033 1013 854 1023 Gas Oil Residue Other Polyethylene (PE) Polypropylene (PP) Polystyrene (PS) Mixture PE/PP/PS Source: Ref.6 9. the heater was started at 298 K and terminated when the desired temperature. Demirbas / J. gas chromatograph (model GC 8000) equipped with a ﬂame ionization detector. TGA curves of PE.9 52.9 styrene – proposed : (1) (2) (3) (4) End-chain scission or depolymerization.8 24. Chain-stripping.6 0. Table 2 Product distribution in plastic pyrolysis (wt. transfer and termination steps . Anal.
5 wt. 3.%. Demirbas / J. Heating rate: 10 K/s. Pyrolysis 72 (2004) 97–102 Fig.3 to 42. Fig. The yields of liquid products increase with increasing pyrolysis temperature up to 750 K and then slightly decrease with temperature increasing from 750 to 900 K.4 wt.% with increasing pyrolysis temperature from 550 to 900 K.8 to 22. the yields of styrene increase from 56 to 64% with increasing pyrolysis temperature from 650 to 750 K and then decrease from 64 to 49. distribution in plastic pyrolysis . 4 shows the yields of the gaseous products from pyrolysis of municipal solid waste. 3. Individual yield of each gas product with increasing pyrolysis temperature is irregular. The yield distributions of the pyrolytic products obtained from PS at different temperatures are shown in Table 3. The yields of liquid products increase with increasing pyrolysis temperature up to 675 K and then slightly decrease from 675 to 850 K.100 A. 4. While pyrolysis temperature increases from 650 to 875 K the yield of C2 –C4 hydrocarbons increases from 3. the yields of gaseous products increase with increasing pyrolysis temperature. 5. From Fig. Fig.6% with increasing pyrolysis temperature from 650 to 875 K. As seen from Fig. . Appl. 5. The residual products from plastic pyrolysis are very low. Curves for yields of the gaseous products from pyrolysis of municipal solid waste. the yields of gaseous products increase from 12. 3. From Table 3. The yield distributions of the pyrolytic products from municipal plastic waste are given in Fig. Curves for yield distributions of pyrolytic products from municipal solid waste. The yield distributions of the pyrolytic products from municipal solid waste are given in Fig. Anal.
8 4.5 6. Light hydrocarbons (LHs) have higher volatilities than those of heavy hydrocarbons (HHc).2 3.0 3.0 6. oleﬁns and aromatics.5 10.5 2.0 5.4 to 10. Adequate volatility is required for smooth operation of petrol engines. Pyrolysis 72 (2004) 97–102 Table 3 Yields of the products obtained by PS pyrolysis at different temperatures (K) Compound Styrene C2 –C4 hydrocarbons C5 –C8 hydrocarbons Methane Toluene Benzene 650 56.5 4.6 22. while pyrolysis temperature Table 4 Yields of the products obtained by PE pyrolysis at different temperatures (K) Fraction Total-parafﬁn Total-oleﬁn Naphthene Aromatics Others 675 35. From Table 5.6 42. Relationships between temperature and the yields of total-parafﬁn and naphthene are irregular.3 20.6 3.5 6.7 to 35.6 35. From Table 4.2 32.9 1.6 wt. naphthenes and isoalkanes are highly desirable.% with increasing temperature to 875 K.7 7.3 23.6 21.1 3. Anal.8 101 875 49.2 1.4 8.%. Higher octane numbers are preferred in internal combustion engines.4 19.2 13. HHs may not be volatile enough to start the engine when the engine is cold.3 to 31.2 31.%.6 750 64.9 800 31.6 1.5 1. 5.8 6.6 800 58. Appl.3 8.%. Heating rate: 10 K/s.5 wt. However.7 21.%.6 6. while pyrolysis temperature increases from 675 to 875 K the yield of total-parafﬁn fraction increases from 35.8 38.3 4. whereas oleﬁns and n-parafﬁns are less desired.1 6.5 1.1 32.8 5. While pyrolysis temperature increases from 675 to 875 K the yield of aromatics fraction increases from 1.0 12.4 44. hydrocarbons from plastic pyrolysis are not suitable for gasoline usage. While pyrolysis temperature increases from 675 to 725 K the yield of aromatics fraction increases from 7.5 23. aromatics. Table 6 shows the yield distributions of the pyrolytic products obtained from municipal plastic waste at different temperatures.8 21.2 42. Curves for yield distributions of pyrolytic products from municipal plastic waste. Suitable hydrocarbons are in the C5 –C8 range.2 10. while pyrolysis temperature increases from 675 to 875 K the yield of total-oleﬁn fraction decreases from 44.9 15.4 2. Demirbas / J. Table 5 shows the yield distributions of the pyrolytic products obtained from PP at different temperatures.8 0.9 .6 725 31.5 725 61.6 wt.6 to 32. The pyrolysis of plastic wastes produces a whole spectrum of hydrocarbons including parafﬁns.6 Table 5 Yields of the products obtained by PP pyrolysis at different temperatures (K) Fraction Total-parafﬁn Total-oleﬁn Naphthene Aromatics Others 675 30.6 wt.5 1.A.7 1.2 Fig.1 800 43.1 875 33.8 10.7 11.9 to 13.%.8 6.5 13.4 5.6 5.9 39.5 0.8 7.4 7.6 to 44.6 19.6 17. Table 6 Yields of the products obtained by municipal plastic waste pyrolysis at different temperatures (K) Fraction Total-parafﬁn Total-oleﬁn Naphthene Aromatics Others 675 32.2 wt.5 24.2 wt. Octane number a measure of the gasoline quality for prevention of early ignition which leads to cylinder knocks.3 700 59.6 875 29. The yield distributions of the pyrolytic products obtained from PE at different temperatures are shown in Table 4.% and then it decreases to 11.4 725 39.3 675 58.8 17.6 2.5 37.9 18. For gasoline production.0 7.7 3.1 22. LHs may cause vapor lock when the engine is hot.2 7.4 875 44.7 34.4 800 24.6 22.5 9.4 33. While pyrolysis temperature increases from 675 to 875 K the yield of total-oleﬁn fraction decreases from 42.8 4.6 17.2 6.5 7.6 0.2 increases from 675 to 875 K the yield of total-oleﬁn fraction decreases from 37. The total yields of parafﬁns and oleﬁns of PE and PP wastes obtained by pyrolysis are higher than that of PS.2 5.8 1.2 5. As seen from Table 6. Gasoline qualities are usually measured in terms of volatility and octane number of the hydrocarbons.6 wt.0 725 28.4 7.
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